EP3145975B1 - Copolymere aus amin-derivatisiertem polyaryletherketon - Google Patents

Copolymere aus amin-derivatisiertem polyaryletherketon Download PDF

Info

Publication number
EP3145975B1
EP3145975B1 EP15728081.9A EP15728081A EP3145975B1 EP 3145975 B1 EP3145975 B1 EP 3145975B1 EP 15728081 A EP15728081 A EP 15728081A EP 3145975 B1 EP3145975 B1 EP 3145975B1
Authority
EP
European Patent Office
Prior art keywords
copolymer
amine
present disclosure
aromatic
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15728081.9A
Other languages
English (en)
French (fr)
Other versions
EP3145975A1 (de
Inventor
Ian David Henderson Towle
Kaylie Jane SMITH
Pauline Julia Siddons
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ketonex Ltd
Original Assignee
Ketonex Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ketonex Ltd filed Critical Ketonex Ltd
Publication of EP3145975A1 publication Critical patent/EP3145975A1/de
Application granted granted Critical
Publication of EP3145975B1 publication Critical patent/EP3145975B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/16—End groups
    • C08G2261/164—End groups comprising organic end groups
    • C08G2261/1644—End groups comprising organic end groups comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3442—Polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/45—Friedel-Crafts-type

Definitions

  • the present disclosure concerns copolymers of polyaryletherketones (PAEKs or PEKs).
  • PAEKs or PEKs polyaryletherketones
  • it concerns methods for making the PAEK copolymers, particles of the copolymers and methods for adding additional functionality.
  • polyaryletherketones by reference to the structure of the repeating unit (as is standard in polymer chemistry) with families being named according to the sequence of ether (symbolised by "E") and ketone (symbolised by "K”) linkages in the repeat units.
  • E ether
  • K ketone linkages in the repeat units.
  • Copolymers comprising such a repeat unit, together with sulphone-containing unit would be referred to as a PEKK-sulphone copolymer.
  • Polyaryletherketones have a variety of useful properties, such as excellent electrical insulating and mechanical properties at high temperature, high strength, toughness and resistance to heat and chemicals.
  • Such polymers may be amorphous or semi-crystalline. Both types usually exhibit high glass transition temperatures (T g ), while the semi-crystalline forms also exhibit high melting temperatures (T m ).
  • T g glass transition temperatures
  • T m melting temperatures
  • the PEK, PEKK, PEEK, PEEKK and PEKEKK families are of particular interest for use in preparing biomedical implants and implant materials due to their excellent mechanical properties, chemical inertness and resistance to stress cracking.
  • the same materials are also useful in aerospace and many other wide-ranging industrial applications including the preparation of thermoplastic composites.
  • PAEKs have wide-ranging uses due to their excellent mechanical properties, chemical inertness and resistance to stress cracking.
  • some applications of the polymers e.g. those related to the aerospace industry
  • materials which can be used at high temperatures while still retaining their crystallinity at the temperature of use There thus exists a need for materials which can be used at high temperatures while still retaining their crystallinity at the temperature of use.
  • PEK copolymers particularly block copolymers, which have these desired properties.
  • a PEK-imide copolymer the PEK parts crystallise (retaining a lower overall T m ) and the imide parts remain amorphous (giving a high overall T g ).
  • This effect is particularly pronounced for block copolymers, where longer PEK parts will crystallise at their "normal" temperature (retaining a lower overall T m ) and the non-PEK parts remain amorphous (giving a high overall T g ).
  • Random copolymers of ether ketones having different chemical groups incorporated into the monomers are reported in Horner et al., J. Mater. Chem. (1991) 1(2):271-280 which uses an electrophilic process to prepare random copolymers. Similar copolymers and processes are also taught in US patent No. 5,436,310 . These prior art copolymers are produced in the form of a gel which is difficult to process as it requires specialist polymerisation equipment. High temperature nucleophilic routes for making random copolymers are also known. Unfortunately none of the prior art polymers have the desired T g /T m values.
  • the present disclosure provides a method of preparing an amine functionalised (e.g. amine terminated) polyaryletherketone copolymer (e.g. a random or block copolymer), said method comprising the steps of:
  • the present disclosure also provides a method of preparing an amine functionalised (e.g. amine terminated) polyaryletherketone copolymer (e.g. a random or block copolymer), said method comprising:
  • the different types of monomer may be polymerised together (i.e. simultaneously in the same vessel) or apart (i.e. in different vessels and/or subsequent to one another).
  • the former approach is especially suitable for the formation of random copolymers, the latter for block copolymers.
  • polyaryletherketone copolymer a polymer which comprises one or more types of aryletherketone unit and one or more types of non-aryletherketone unit.
  • Aryletherketone units are considered to be parts of the polymer which consist essentially of aryl groups linked by ether and ketone groups.
  • the non-aryletherketone units are one or more units which comprise moieties other than aryl groups, ether groups and ketone groups (although aryl, ether and/or ketone groups may also be present).
  • the monomer system suitable for forming aryletherketone units may be replaced by one or more monomers which consists essentially of aryl and ketone groups or consists essentially of aryl and ether groups, preferably one consisting of aryl and ketone groups, especially a "KK" unit such as a phthaloyl halide as herein described.
  • the comonomer which comprises non-aryletherketone units should contain ether linkages such that the eventual copolymer contains both ether and ketone linkages.
  • the copolymers may be random or block copolymers depending on their arrangement of aryletherketone units and non-aryletherketone (i.e. those formed by the comonomer) units.
  • Block copolymers of the present disclosure are considered to be those comprising blocks of at least 2, preferably 2 to 20, especially 3 to 10, e.g. at least 4 aryletherketone units and/or at least 2, preferably 2 to 20, especially 3 to 10, e.g. at least 4 non-aryletherketone units.
  • block copolymers are particularly preferred due to their effects on the T g and T m values. It is typically believed that the crystalline state of the polymer does not affect the T g and so a single T g is typically quoted, irrespective of the crystalline state of a polymer. However, for some of the block copolymers of the present disclosure the difference in the amorphous and crystalline T g can be 20 to 30°C, which is unexpected. Certain polyaryletherketone block copolymers are hitherto unknown and thus form a further aspect of the present disclosure.
  • the present disclosure also provides a method of preparing an amine functionalised (e.g. amine terminated) polyaryletherketone block copolymer, said method comprising:
  • the random copolymers of the prior art are made by mixing all the materials together almost simultaneously.
  • the fact that the processes of the present disclosure can be carried out at relatively low temperatures renders the present disclosure particularly useful for the production of block copolymers as the different (e.g. two or more) types of monomer can be added sequentially by opening the reactor once the first component has reacted.
  • the high temperatures (e.g. 350 °C) required for nucleophilic processes render this opening of the reactor problematic (e.g. for safety reasons), the low temperature processes of the present disclosure solve this problem.
  • the different types of monomer may be polymerised in separate reaction vessels before being combined to form a block copolymer.
  • the monomer system suitable for forming aryletherketone units is polymerised before, after, or at the same time as, the comonomer (i.e. the unit or units which form the non-aryletherketone units of the copolymers of the present disclosure).
  • the monomer system suitable for forming aryletherketone units may be polymerised in the same vessel or a different vessel to polymerisation of the comonomer
  • all types of monomer may be added and/or polymerised together, i.e. they are polymerised simultaneously in the same vessel.
  • block copolymers the types of monomer are polymerised separately, e.g. at different times and/or in different vessels.
  • At least one type of monomer is added after at least one other has polymerised, e.g. the monomer system suitable for forming aryletherketone units is polymerised before or after the comonomer (or vice versa).
  • the monomers i.e. (i) and (ii) are polymerised in different vessels and then mixed together to form the copolymers of the present disclosure.
  • the monomer system suitable for forming aryletherketone units is polymerised before the comonomer is added to the reaction medium, or the comonomer is polymerised before the monomer system suitable for forming aryletherketone units is added to the reaction medium.
  • the monomers are polymerised in different vessels prior to mixing to form the copolymers of the present disclosure.
  • non-aryletherketone units of the copolymers are incorporated into the copolymer via one or more types of comonomer which comprise at least one moiety which is not an aryl, ether or ketone moiety.
  • these comonomers will contain ether groups to activate the para carbon to electrophilic attack. Examples of such comonomers, in all aspects of the present disclosure described herein are those comprising ester, imide, sulphone and/or amide groups.
  • the present disclosure provides a method of preparing an amine functionalised (e.g. amine terminated) polyaryletherketone copolymer (e.g. a random or block copolymer), said method comprising:
  • aryletherketone units of the copolymers of the present disclosure in all aspects of the present disclosure described herein, include, but are not limited to the following (and combinations thereof):
  • copolymers comprising EKEKK units are less preferred.
  • the aryletherketone component of the copolymers of the present disclosure comprises one or more types of aryletherketone unit, e.g. one or more of EK, EKK, EEK, EEKK and EKEKK.
  • non-aryletherketone units of the copolymers of the present disclosure may comprise one or more types of non-aryletherketone units, e.g. one or more units selected from those comprising ester, imide, sulphone and/or amide groups.
  • aryletherketone unit and non-aryletherketone unit can take place within one unit (e.g. -EK-EKK-imide), and/or throughout the copolymer (e.g. - EK-imide-EKK-imide).
  • one unit e.g. -EK-EKK-imide
  • the copolymer e.g. - EK-imide-EKK-imide
  • only one or two, especially one type of aryletherketone unit and or one or two, especially one type of non-aryletherketone unit is present in the copolymer.
  • the units themselves need not be totally identical, although they preferably are.
  • the two imide-containing units need not be identical and nor do the aromatic groups of the EK and EKK units.
  • the aryletherketone units are identical throughout the polymer, as are the non-aryletherketone units.
  • copolymers including any combination of the monomers herein described to be produced, e.g. a copolymer comprising several types of monomer such as an ether-ketone-imide-ester-amide-sulphone-copolymer could be made if desired.
  • Particularly preferred copolymers are those comprising the following combinations of comonomers (in combination with one or more aryletherketone units as herein described):
  • references to copolymers comprising a particular combination of units should be understood to encompass polymers containing one or more of said combination of units, as well as polymers consisting of, or consisting essentially of, said combination of units.
  • the present disclosure enables to production of copolymers with a variety of useful properties. Yet further functionality is added by incorporating amine groups into the polymers.
  • amine-functionalised (e.g. amine-terminated) PEK copolymers can be produced using a process in which the reactive amine end-cap is protected during the reaction and subsequently de-protected during the final work-up.
  • the invention thus conveniently enables the addition of amine groups when performing the polymerisation reaction, i.e., no additional steps are required on order to achieve amine functionalisation.
  • the use of protecting groups is common in pharmaceutical organic chemistry, but is generally avoided in polymer chemistry and other industrial applications due to the additional cost and complexity it can add to a process.
  • R is either an aliphatic or aromatic group and is defined below.
  • the method is preferably a single-step reaction, i.e., no additional steps before or after polymerisation are required in order to achieve amine functionalisation.
  • the term "functionalised” is intended to encompass polymers with one or more amine functional groups as end-groups. It also encompasses polymers in which the amine groups are substituents on the polymer chain, i.e. pendant to the backbone. Preferably, the polymers are functionalised at the end groups.
  • the polymers of the present disclosure may be "functionalised” insofar as they comprise one or more amine groups as end groups, i.e. at one or more ends of the polymer chain and/or as pendant groups, i.e. at one or more positions along the polymer backbone.
  • the term “functionalised” is therefore intended to encompass amine groups on the particles, at least some of which have the potential to bond with other materials, e.g. other monomers in formulations.
  • the functional groups for the polymers of the present disclosure are amines, i.e. - NR 2 , NRH or -NH 2 , preferably NRH or -NH 2 , especially -NH 2 , and derivatives thereof, where "R" is either an aliphatic or aromatic group. Where R is an aromatic group, it is preferably Ar as herein described (especially phenyl). Where R of -NR 2 or NRH is an aliphatic group, it is preferably selected from alkyl groups, e.g. C1-6 aliphatic groups, especially methyl or ethyl groups.
  • the compounds described herein in which the functional group is protected i.e. those functionalised by protected amine groups as described herein, form a further aspect of the present disclosure.
  • amine functionalisation is also encompassed, e.g. where a phenyl ring at the end of the polymer has more than one, i.e. 1 to 5 amine groups thereon.
  • the polymers of the present disclosure are terminated with an amine group, i.e. an amine group is found on at least one end of the polymer chain.
  • an amine group is found on at least one end of the polymer chain.
  • at least 50% of the end groups, i.e. the ends of the polymer chains are amine-functionalised, preferably at least 70%, especially preferably at least 85%, e.g. at least 95%.
  • substantially all chain ends comprise an amine group.
  • Amine-terminated polymers are particularly preferred.
  • the amine groups may be pendant to the polymer chain, i.e. they are substituents of the polymer's aromatic moieties.
  • 0 to 100% of the Ar groups preferably 25 to 75%, i.e. around 50% of the Ar groups are substituted with an amine group.
  • the amine groups of the present disclosure may be situated on aryl groups which themselves are attached to ketone and/or ether linkages of the polymer. In a less preferred aspect, there may be a linker group between the aryl group of the polymer chain and the amine group.
  • the polymers of the present disclosure may be blended with one another or with other types of polymer to form polymer blends.
  • Each aromatic moiety in the polymer repeating unit (Ar) may be independently selected from substituted and unsubstituted mononuclear aromatic moieties (e.g. phenylene) and substituted and unsubstituted polynuclear aromatic moieties.
  • polynuclear is considered to encompass fused aromatic rings such as naphthalene and non-fused rings such as biphenyl, etc.
  • Ar is phenylene (Ph) e.g. unsubstituted phenylene.
  • phenylene and polynuclear aromatic moieties may contain substituents on the aromatic rings. Such substituents would be readily understood by the skilled person and should not inhibit or otherwise interfere with the polymerisation reaction to any significant extent.
  • Typical substituents may include, for example, phenyl, halogen (e.g. F, Cl, Br, I), ester, nitro, cyano and the like.
  • the substituents are preferably pendant to the chains, rather than in the backbone, i.e. not bonded to a carbonyl carbon atom of a ketone linkage nor to an oxygen atom of an ether linkage.
  • the ketone linkages i.e. the carbon atoms of the carbonyl group
  • the oxygen atoms of the ether linkages are preferably attached to carbon atoms, especially to aromatic carbon atoms of adjacent aromatic groups.
  • Linear copolymers are preferred, however cross-linked polymers are also encompassed.
  • Cross-linked polymers may be produced by using cross-linking agents and/or suitable monomers containing more than two (i.e. 3, 4, 5 or 6) ether or carboxylic acid halide (e.g. chloride) groups in the methods of the present disclosure.
  • Examples of such monomers and agents include benzene-1,3,5-tricarbonyl chloride; 1,3,5-triphenoxy benzene; benzene-2,3,5,6-tetracarbonyl chloride; benzene-1,2,3,4,5,6-hexacarbonyl chloride; 1,2,3,4,5,6-hexaphenoxy benzene; naphthalene-1,4,5,8-tetracarbonyl chloride, triphenoxybenzene, benzenetricarboxylic acid chloride, hexaphenyl benzene and the like.
  • These monomers or agents are typically used in relatively low concentrations, e.g. from 0.5M% to 25M%, or between 0.5M% and 25M%.
  • the compounds of the present disclosure are linear and terminated with a functional group.
  • Oligomeric analogues of the copolymers of the present disclosure form a further aspect of the present disclosure.
  • the processes herein described are also applicable to oligomers.
  • the present disclosure provides oligomer derivatives of the polyaryletherketone copolymers herein described and processes for their production, e.g. oligomers comprising one or more polyaryletherketone units as herein described and one or more non-polyaryletherketone units as herein described. Where more than one ether-ketone unit is present, the compound may be monofunctional, bifunctional, trifunctional or multifunctional.
  • X is a non-polyaryletherketone unit as herein described, e.g. a unit comprising an ester, amide, imide and/or sulphone moiety and E is either an end group or an amine functional group or protected amine as herein described, especially -NH 2 .
  • the functionalised compounds of the present disclosure are produced using a process which involves use of a capping agent.
  • the capping agent comprises -NR 2 , -NRH or a protected version of the amine group which is intended to functionalise the copolymer, monomer or oligomer.
  • Certain protected capping agents are novel and form a further aspect of the present disclosure.
  • the capping agent comprises a protected amine group.
  • the capping agents of the present disclosure therefore comprise, e.g. include, -NR 2 ,-NRH or protected amine functional groups (preferably protected amine groups), the protecting group functioning to protect the eventual amine groups during polymerisation.
  • capping agent comprising a -NR 2 , -NRH or a protected amine
  • Capping agents comprising leaving groups are especially preferred.
  • Capping agents comprising hydroxyl groups (-OH) are less preferred.
  • Especially suitable capping agents of the present disclosure are of general formula (Z) a -Ar-(X) b wherein:
  • Z is NL 2
  • the two leaving groups can be linked to form an imide, e.g. Z is of the following structure:
  • Y is a linker group, especially an aryl group (especially phenyl), -(CH 2 ) n - or-(CF 2 ) n -, where n is an integer, preferably 2 to 6.
  • a preferred capping agent of this type is the following, which is available from Molport.
  • R is an aromatic group, it is preferably Ar as herein described (especially phenyl).
  • R is an aliphatic group, it is preferably selected from alkyl groups, e.g. C1-6 aliphatic groups, especially methyl or ethyl groups
  • each R group is independently as defined herein, i.e. R is independently selected from an aliphatic or aromatic (e.g. Ph) group, preferably aliphatic, e. g. alkyl groups, e.g. C1-6 aliphatic groups, especially methyl or ethyl groups.
  • R is independently selected from an aliphatic or aromatic (e.g. Ph) group, preferably aliphatic, e. g. alkyl groups, e.g. C1-6 aliphatic groups, especially methyl or ethyl groups.
  • the capping agent is of formula Z-Ph-O-Ph.
  • Z is a haloacetyl protected amine group, e.g. -NH n R, especially, a trifluoroacetamide group.
  • Preferred capping agents include the following compound and its acetyl equivalent, i.e. compounds of the above formula where n is 1, Ar is Ph and R is acetyl or trifluoroacetyl:
  • CF 3 -EC 2,2,2-trifluoro-N-(4-phenoxyphenyl)acetamide
  • the trifluoroacetyl group has been found to be particularly easy to remove during the acid/base work-up.
  • the capping agents of the present disclosure can be prepared from readily available materials such as aminobenzoic acid, diaminobenzoic acid and diphenylether.
  • a functionalised monomer is used.
  • the amine functional group of the monomer must be protected in order to avoid unstable amide linkages being formed.
  • Suitable monomers are iso- or tere-phthalic acid chlorides comprising protected amine groups as described above.
  • the amine group of 5-aminoisophthalic acid may be protected prior to conversion of the molecule to the acid chloride. This can then be used in place of some of the terephthaloyl or isophthaloyl chloride monomers when preparing the PAEK copolymers of the present disclosure.
  • An advantageous feature of the processes of the present disclosure is that the leaving group of the capping agent (i.e. L) is removed during standard work-up procedures following the polymerisation. There is thus no need for a separate "deprotection" step.
  • Typical work-up conditions which result in removal of the leaving group are the use of water, or acidic/basic aqueous solutions, e.g. solutions of HCI or NaOH.
  • the water or solution is typically at a temperature of 0 to 100 °C at atmospheric pressure, preferably 20 to 100 °C, e.g. 50 to 80 °C.
  • work-up can take place under pressurised conditions, e.g. at pressures of 200 kPa.
  • a representative workup procedure for a PEKK polymerisation carried out in a one litre reactor is as follows:
  • the monomer system used in the methods herein described comprises monomers suitable for co-polymerisation in order to produce a polyaryletherketone copolymer, e.g. a polymer comprising aryl groups linked via ether linkages, ketone linkages and at least one other type of linkage that is neither an ether nor a ketone.
  • a polyaryletherketone copolymer e.g. a polymer comprising aryl groups linked via ether linkages, ketone linkages and at least one other type of linkage that is neither an ether nor a ketone.
  • Preferred monomers may include but are not restricted to:
  • At least one of R1 and R3 is the branch unit: Where branched units are present, they are preferably present in a molar percentage of 0.5% to 25% (i.e. 0.5 to 25M%).
  • Preferred monomers may include iso and terephthaloyl halides and phthaloyl halides (i.e. the 1,2 substituted version), preferably iso and terephthaloyl halides, preferably chlorides and 1,4-bis(4-phenoxybenzoyl)benzene.
  • Especially preferred monomers are the following: TPC IPC NAC (numbers will give the positions of the substitution e.g 2,6 or 1,4) EKE ESE EKKE EIEIE EIKIE EISIE EI-IE EI6FIE EINIE EKNKE
  • Preferred monomers for the production of the copolymers of the present disclosure include the following (i.e. the copolymer comprises an aryletherketone repeat unit and one or more of the following repeat units): OR -C(CF 3 ) 2 -
  • the comonomer does not contain a five-membered ring.
  • the only rings present in the polymer backbone are aryl groups as herein described.
  • the reaction medium comprises, in addition to the Lewis acid and the controlling agent (and optional capping agent) a compound comprising an aromatic moiety and more than one reactive carbonyl group (e.g. more than one carboxylic acid halide group).
  • this compound can be used as an alternative to the monomer system suitable for forming aryletherketone linkages.
  • Such compounds facilitate reaction between the aryletherketone and non-aryletherketone components of the copolymers and are especially preferred where one or more of the monomers are not self-polymerising.
  • Suitable compounds include multifunctional (especially difunctional or trifunctional) aromatic carboxylic acid halides, especially aromatic di- or tri-carboxylic acid halides, e.g. one or more of the following (where Cl is preferred but may be replaced by any other halide):
  • Particularly preferred compounds for this aspect are iso and terephthaloyl halides, preferably chlorides. This aspect of the present disclosure is especially preferred where one or more of the monomers is not self-polymerising as the ketone groups of the monomer participate in the reaction.
  • chlorides Whilst the above-listed chlorides are preferred, other acid halides, particularly the fluorides and the bromides, may also be used. Generally, the chlorides are preferred due to their availability and reactivity. Other groups that are potentially displaceable under Friedel-Crafts conditions may also be used. These might include groups such as -OR, where R is methyl, ethyl, isopropyl or other lower alkyl.
  • monomers with repeating units "EKK" can be polymerised alone, to produce PEKK parts of the copolymers of the present disclosure.
  • the proportion of 1,4-linked aromatic (e.g. phenyl) rings in polyaryletherketones greatly influences the characteristics of the resulting polymer and the size of the particles formed (e.g. its processability, glass transition temperature and its crystalline melting point, even to the extent of producing an amorphous PEKK etc.).
  • the characteristics can be modified by changing the proportion of 1,4-linked aromatic rings in the polymer. This may be achieved by the use of monomers comprising 1,3-substituted aromatic rings.
  • isophthaloyl halides such as isophthaloyl chloride can be used as monomers and the amounts chosen in relation to the other monomers in order to produce a polymer with the desired characteristics.
  • the monomers are chosen such that the proportion of 1,3-linked aromatic rings in the resulting polymer is 0 to 100%, more especially 5 to 50%, particularly 20 to 40%, e.g. about 30%. All percentages and ratios are by weight, unless otherwise specified.
  • the proportion of 1,4 (tere-, or "T") to 1,3 (iso-, or "I")-linked aromatic rings in the resulting polymer can also be represented as a tere-:iso-, or "T:I” ratio and is preferably within the range of 100:0 to 60:40.
  • the monomer system suitable for forming aryletherketone units comprises bis 1,4-(4-phenoxybenzoyl)benzene and terephthaloyl halide and isophthaloyl halides (e.g. a 60:40 mixture of tere- and iso-phthaloyl chloride) in a 1:1 ratio by weight.
  • the ratio (e.g. molar ratio) of aryketherketone units to non-aryletherketone units in the polymers and oligomers of the present disclosure is in the range of 1:99 to 99:1, e.g. 20:80 to 80:20, especially 30:70 to 70:30, 40:60 to 60:40 or 50:50.
  • the most preferable ratios are 30:70 and 70:30.
  • the temperature at which the reaction is conducted can be from about -50 °C to about +150 °C. It is preferred to start the reaction at lower temperatures, for example at about -50 °C to about -10 °C, particularly if the monomer system contains highly reactive monomers. After polymerisation has commenced, the temperature can be raised if desired, for example, to increase the rate of reaction. It is generally preferred to carry out the reaction at temperatures in the range of between about -30 °C and +25 °C, particularly +20 °C.
  • the processes of the present disclosure can be carried out at relatively low temperatures renders the present disclosure are particularly useful for the production of block copolymers as the two (or more) types of monomer can be added sequentially by opening the reactor once the first component has reacted.
  • the high temperatures e.g. 350 °C
  • nucleophilic processes render this opening of the reactor problematic (e.g. for safety reasons)
  • the low temperature processes of the present disclosure solve this problem.
  • the first monomer system is polymerised (in the presence of the Lewis acid and the controlling agent).
  • the other monomers can be added (following optional cooling to e.g. +5 °C). Addition of further monomers is ideally carried out gradually so as to prevent the reaction temperature rising excessively.
  • the controlling agent is an aromatic carboxylic acid, aromatic sulphonic acid or derivatives thereof.
  • Such acids may comprise 1, 2 or 3 carboxylic or sulphonic acid groups on an aromatic ring (i.e. these may be mono-, di- or tri-acids).
  • Derivatives of such acids include metals salts and esters.
  • Preferred controlling agents for use in the method of the present disclosure include the following: (i) Ar'(COOX) y ; (ii) Ar'(SO 3 X) y ; (iii) (Ar'COO - ) z M z+ ; or (iv) (Ar'SO 3 - ) z M z+
  • the aromatic group of the controlling agent may be selected from substituted and unsubstituted mononuclear (e.g. phenyl) and substituted and unsubstituted polynuclear aromatic moieties.
  • the aromatic group of the controlling agent is an optionally substituted phenyl group.
  • Preferred substituents may include halogen (e.g. F, CI, Br, I), nitro, cyano, alkyl (e.g. C 1-6 alkyl) and the like.
  • Alkyl substituents are preferred, e.g. methyl, ethyl, etc. Where substituents are present, these are preferably electron-withdrawing groups which deactivate the ring to electrophilic attack.
  • the organic group R is preferably a straight-chained or branched C 1-6 alkyl group, i.e. the controlling agent is an alkyl ester of an aromatic carboxylic acid or aromatic sulphonic acid. More preferably, R is C 1-4 alkyl. e.g. methyl.
  • controlling agents for use in the present disclosure include benzoic acid, chlorobenzoic acid (e.g. 4-chloro benzoic acid), methyl benzoic acid (e.g. 4-methyl benzoic acid), sodium benzoate, magnesium benzoate, aluminium benzoate, methyl benzoate and benzene sulphonic acid.
  • the controlling agent is benzoic acid.
  • Mixtures of two or more controlling agents may also be used, if desired.
  • the amount of controlling/dispersing agent present is preferably from 0.1 to 6 equivalents per equivalent of acid halide groups present in the monomer system.
  • Typical ranges of ratio of moles of controlling agent to moles of acid halide groups present in the monomer system are from 0.1 to 10, preferably 0.5 to 7, especially 0.7 to 5, particularly preferably 1.5 to 2.
  • Amounts greater than 5 equivalents could be employed, if desired, e.g. up to 10 equivalents, e.g. 7 equivalents.
  • no additional controlling or dispersing effect is usually achieved by adding larger amounts and it generally means that more Lewis acid is also required.
  • no more than 5 equivalents more preferably between 0.5 and 4 equivalents and especially 1 to 3 or between 0.5 and 2 or 2 to 4 (e.g. 2 to 3) equivalents per equivalent of acid halide groups.
  • a particularly preferred amount of controlling agent is 2 equivalents per equivalent of acid halide groups.
  • controlling agent added depends upon, inter alia , the particular controlling agent used, the nature of the monomers present and the type and amount of Lewis acid employed.
  • the ranges given particularly apply to the controlling agents containing one acid or base acid functionality, e.g., those listed as (i) to (iv) above where y or z is equal to 1.
  • controlling agents containing more than one acid or base group per molecule e.g. where y or z is not 1
  • the equivalents of controlling agent to acid halide groups in the monomer systems may be adjusted accordingly.
  • controlling agents such as benzoic acid can also be readily recovered for future use when carrying out the methods of the present disclosure.
  • the recovery of the controlling agent benzoic acid is facilitated by the fact that the acid has very low solubility in cold water but high solubility in hot water.
  • the polymer can be recovered by filtration and on allowing the filtrate to cool the benzoic acid crystallises out facilitating its recovery for future use.
  • An alternative method to recover the benzoic acid would be to add sufficient sodium hydroxide to form sodium benzoate which is water soluble (1g in 2mL of water), filter and isolate the polymer and then add an acid such as hydrochloric acid to the filtrate to reform benzoic acid which would precipitate from the filtrate.
  • a further advantage of the present disclosure is the reduction in the amount of water necessary to remove the catalyst residues and controlling agents when compared to that necessary using the gel and tube process.
  • the polymer after decomplexation has a very low bulk density, sometimes as low as 0.08 g/mL, thus requiring the use of large work-up vessels and large quantities of water to afford a mobile slurry.
  • the dispersion method of the present disclosure i.e. that involving an aromatic carboxylic acid or aromatic sulphonic acid or derivatives thereof as controlling agent
  • the bulk density of the isolated polymer is much higher thus permitting the use of much lower volume work-up vessels and significantly reducing the amount of water required to purify the isolated polymer.
  • capping agents which do not contain an amine group may be added to the polymerisation reaction medium to cap the polymer on at least one end of the polymer chain. This terminates continued growth of that chain and controls the resulting molecular weight of the polymer. Use of these capping agents may therefore be used to produce polymers within a selected narrow molecular weight range. In this aspect, both nucleophilic and electrophilic capping agents may be used to cap the polymer at each end of the chain. Such capping agents may be used in addition to, or as an alternative to, the capping agent which comprises -NR 2 , -NRH or a protected amine, which is used to produce the functionalised compounds of the present disclosure.
  • Preferred nucleophilic capping agents of this type are 4-chlorobiphenyl, 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone, biphenyl 4-benzenesulphonylphenyl phenyl ether, and the like.
  • Typical electrophilic capping agents include benzoyl chloride, benzenesulfonyl chloride and the like.
  • TPC terephthaloyl chloride
  • IPC isophthaloyl chloride
  • a Lewis acid is used as catalyst.
  • the term "Lewis acid” is used to refer to a substance which can accept a shared electron pair from another molecule.
  • Suitable catalysts for use in the method of the present disclosure include aluminium trichloride, aluminium tribromide, antimony pentachloride, antimony pentafluoride, indium trichloride, gallium trichloride, boron trichloride, boron trifluoride, zinc chloride, ferric chloride, stannic chloride, titanium tetrachloride, and molybdenum pentachloride.
  • the catalyst is substantially anhydrous aluminium trichloride.
  • the amount of Lewis acid catalyst used will vary depending on the particular monomers and the reaction medium selected. Typically, the amount of Lewis acid required is calculated on the basis of one Lewis acid for each ketone unit, plus an amount equimolar to that of Lewis base, or controlling agent, plus up to 20% excess. Larger excesses can be used but offer no significant advantage.
  • Alternative catalyst systems for electrophilic processes include use of trifluoromethanesulphonic acid, with and without P 2 O 5 , and those using mixtures of CF 3 -COOH and CF 3 -SO 3 H with and without P 2 O 5 .
  • Terephthalic and isophthalic acids can be used in these super acid mixtures.
  • PEKK can be produced from EKKE plus terephthalic and isophthalic acids in CF 3 -SO 3 H, with the CF 3 -SO 3 H is used as the solvent.
  • the CF 3 -SO 3 H reacts with the tere/iso acids to give the mixed carboxylic-sulphonic anhydride CF 3 -SO 2 -O-CO-Ph-CO-O-SO 2 -CF 3 which in the presence of an electron rich -H group as in EKKE then eliminate CF 3 -SO 3 H and forms a ketone unit.
  • CF 3 -SO 3 H CF 3 -COOH with some CF 3 -SO 3 H plus P 2 O 5 to remove the water produced may be used.
  • Preferred solvents for the electrophilic polymerisation reaction are halogenated hydrocarbons (e.g. tetrachloroethylene, 1,2,4-trichlorobenzene, o-difluorobenzene, 2-dichloroethane dichlorobenzene, 1,1,2,2,-tetrachloroethane, particularly ortho-dichlorobenzene, dichloromethane etc.).
  • non-chlorinated diluents may be used such as cyclohexane, carbon disulphide, nitromethane, nitrobenzene, HF.
  • Dichloromethane (DCM) is particularly preferred for use in the present disclosure.
  • a non-protic diluent can also be employed, if desired.
  • the diluent should be inert towards Friedel-Crafts reactions.
  • Other diluents include, for example, dichloromethane, carbon disulphide, o-dichlorobenzene (i.e. ortho- or 1,2-dichlorobenzene), 1,2,4-trichlorobenzene, o-difluorobenzene, 1,2-dichloroethane, cyclohexane, 1,1,2,2,-tetrachloroethane and mixtures thereof. Whilst these additional diluents may be used they confer no significant advantage to the process and may result in difficulty in separating the diluents used for further use. A process which is substantially free from co-solvent is therefore a preferred aspect of the present disclosure.
  • the amount of any diluent used is most preferably in the range of 10 mL to 400 mL, especially 50 mL to 200 mL of diluent to 10 g of polymer. Both higher and lower concentrations (preferably higher) may be used if required.
  • the polymer When electrophilic polymerisation is complete, the polymer contains Lewis acid catalyst complexed to any carbonyl groups (and possibly also to ether groups).
  • the catalyst residue must be removed, i.e. the Lewis acid must be decomplexed from the polymer and removed.
  • Decomplexation can be accomplished by treating the polymerization reaction mixture with a decomplexing base after completion of polymerization.
  • the decomplexing base must be at least as basic towards the Lewis acid as the basic groups on the polymer chain.
  • the amount of decomplexing base used should be in excess of the total amount of bound (complexed) and unbound Lewis acid present in the reaction mixture and is preferably at least twice the total amount of Lewis acid.
  • Typical decomplexing bases which can be used include water, dilute aqueous hydrochloric acid, methanol, ethanol, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, pyridine, dimethyl ether, diethyl ether, tetrahydrofuran, trimethylamine, trimethylamine hydrochloride, dimethyl sulphide, tetramethylene sulphone, benzophenone, tetramethylammonium chloride, isopropanol, acetic acid and the like. Iced water or cooled dilute hydrochloric acid are preferred for use in the present disclosure.
  • the electrophilic process can be carried out in a manner similar to standard suspension polymerisation reactions.
  • the reactions are generally carried out in a dry and/or inert, preferably dry, especially dry and inert atmosphere, e.g. reaction vessels may be purged with dry air, nitrogen, argon or CO 2 .
  • the catalyst e.g. AlCl 3
  • the cooled solvent preferably dichloromethane, preferably cooled to well below room temperature, e.g. -20°C
  • the controlling agent preferably benzoic acid
  • monomers and (optional) end-capper may then be added in a solution of the same solvent or as solids.
  • the controlling agent may be added earlier or later in the sequence of additions, preferably after the catalyst and before the monomers, provided the temperature of the slurry is kept below -10 °C during the addition, preferably below -20 °C. Additional reaction components, e.g. capping agents, additional diluent etc., are typically also added at this stage. If used, the capping agent can be added later, even after the mixture has warmed. This has the effect of altering the molecular weight distribution which can be advantageous in some instances.
  • the Lewis acid is added to the reaction medium prior to the controlling agent.
  • the components are added to the reaction medium in the following order:
  • the monomer system suitable for forming aryletherketone units is polymerised before, after, or at the same time as, the comonomer. Moreover, the monomer system suitable for forming aryletherketone units is polymerised in the same vessel or a different vessel to polymerisation of the comonomer For the formation of random copolymers, all types of monomer may be added and/or polymerised together. For the formation of block copolymers, at least one type of monomer is added after at least one other has polymerised, e.g. the monomer system suitable for forming aryletherketone units is polymerised before or after the comonomer. Alternatively, in an embodiment especially suited to the formation of block copolymers, for the formation of block copolymers, different monomers are polymerised in different vessels and then mixed together to form the copolymers of the present disclosure.
  • the resulting reaction mass is then typically allowed to warm towards room temperature while being stirred vigorously in a suitably baffled reactor.
  • any by-products e.g. condensation products
  • decomplexing base e.g. iced water
  • work-up/decomplexation can begin by combining the entire reaction mass with decomplexing base (e.g. iced water). Care must be taken to avoid the temperature of the decomplexing mixture rising above room temperature (+25 °C).
  • decomplexing base e.g. iced water
  • the reaction mass Prior to decomplexation the reaction mass is typically an orange slurry and after complete decomplexation the mass is usually a snow white/off white slurry.
  • the mass is then typically stirred at or below room temperature to yield the final polymer product.
  • Solvent removal from this product may be carried out by any conventional method, although typically this will be by distillation. Further purification can be achieved by known methods, e.g. hot filtration of the suspension to yield the polymer product, typically as a snow white/ off white residue. Cooling of the combined filtrates, including any acidic washes (e.g. to 5°C) results in recovery of any benzoic acid used as the controlling agent by crystallisation. Using these methods, up to 95% of the solvent, usually dichloromethane, can be recovered along with up to 90% of the controlling agent (e.g. when the controlling agent is benzoic acid or a benzoic acid derivative).
  • the polymers produced by way of the methods herein described are considered to form a further aspect of the present disclosure.
  • the present disclosure provides an amine-functionalised polyaryletherketone copolymer obtainable by any process as herein described.
  • the present disclosure provides, for the first time, a method for the production of amine-functionalised polyaryletherketone block copolymers.
  • Amine-functionalised polyaryletherketone block copolymers therefore form a further aspect of the present disclosure.
  • the present disclosure provides, for the first time, a method for the production of amine-functionalised polyaryletherketone copolymers.
  • Amine-functionalised polyaryletherketone copolymers wherein said copolymer is neither an amine functionalised PEK-imide copolymer nor an amine functionalised PEK-sulphone copolymer, therefore form a further aspect of the present disclosure.
  • a further advantage of the present disclosure is that the process can yield polymer particles, e.g. spheres of polyaryletherketone copolymers.
  • the provision of spherical particles directly from the polymer production process is particularly advantageous as it means that costly further processing steps such as grinding and sieving are not necessary. Instead, the process gives spherical particles directly.
  • the spherical particles produced according to the present disclosure are more uniform in shape rather than the rough particulates that would be produced by grinding.
  • Particles of amine- functionalised polyaryletherketone copolymers have, until now, been unobtainable, and thus form a further aspect of the present disclosure. Therefore, viewed from a further aspect, the present disclosure provides particles, e.g. spherical or substantially spherical particles of the amine-functionalisedpolyaryletherketone copolymers of the present disclosure.
  • the polymer morphology is in a semi-crystalline state with the degree of crystallinity greater than 5% to impart good chemical resistance and low moisture pick-up.
  • the particles' physical structure may range from being solid (high density; e.g. density of 1.3 g/cc or greater) to cellular (density of ⁇ 1 g/cc) structure, or a combination of the two.
  • particle size is meant particle diameter.
  • the particles according to the present disclosure advantageously have particle sizes (e.g. as measured with a Malvern Mastersizer particle size analyser) of 0.1 to 3000 ⁇ m, preferably 1 to 500 ⁇ m, especially preferably 1 to 100 ⁇ m, particularly 10 to 200 ⁇ m, e.g. 50 to 100 ⁇ m.
  • the particles Preferably have one dimension that is 75 ⁇ m or less, e.g. 10 to 50 ⁇ m.
  • the particles are substantially spherical particles having diameter of less than 75 ⁇ m.
  • the particles are substantially spherical in shape with an aspect ratio (R) of about 1 to 1.5.
  • At least 25% (by volume) of the particles are less than 100 ⁇ m in diameter, preferably at least 50%, e.g. at least 75%.
  • at least 20% of the particles are less than 70 ⁇ m, preferably at least 40%, e.g. at least 60%.
  • the particles preferably have a coefficient of variation (CV) of less than 20%, e.g. less than 10%, more preferably less than 5%, still more preferably less than 2%.
  • CV is preferably calculated on the main mode, i. e. by fitting a monomodal distribution curve to the detected particle size distribution. Thus some particles below or above mode size may be discounted in the calculation which may for example be based on about 90% of total particle number (of detectable particles that is).
  • Such a determination of CV is performable on a Malvern Mastersizer particle size analyser or a Malvern Mastersizer particle size analyser.
  • the polymers or copolymers of the present disclosure have a weight average molecular weight (Mw) of at least 8,000, preferably greater than 9,000, especially greater than 10,000, more specifically, in the range of 8,000 - 162,000, more preferably, 26,000 - 162,000.
  • Mw weight average molecular weight
  • the M w as disclosed herein can be determined by gel permeation chromatography (GPC).
  • the polymers or copolymers of the present disclosure have an inherent viscosity (IV) of at least 0.2 dl/g, e.g. at least 0.28 dl/g, especially at least 0.4 dl/g, particularly preferably at least 0.5 dl/g.
  • IV inherent viscosity
  • Preferred ranges are 0.4 -1.7 dl/g, e.g. 0.6 - 1.5 dl/g. IV as discussed herein can be measured by using a conventional viscometer.
  • the polymers or copolymers of the present disclosure have a glass transition temperature (T g ) of at least 140 °C as measured by differential scanning calorimetry (DSC), more specifically, in the range of 140 -178, especially at least 144 °C, particularly preferably at least 148 °C, e.g. 158 -178 °C.
  • T g glass transition temperature
  • DSC differential scanning calorimetry
  • the size of the polymer particles may be controlled by varying the amount of dispersant (i.e. controlling agent) added, amount of polymer per unit volume of solvent, the stirrer speed, the stirrer paddle design, temperature ramp rate, the reactor design and/or the addition of baffles to create turbulence.
  • dispersant i.e. controlling agent
  • Other techniques well known in dispersion polymer chemistry may be employed.
  • the present inventor has surprisingly found that, not only can the present disclosure provide spherical particles of polyaryletherketone copolymers for the first time, but the method allows the particle size (e.g. distribution and/or mean) to be controlled by varying the amount of controlling agent used.
  • controlling agent added depends upon, inter alia , the particular controlling agent used, the nature of the monomers present and the type and amount of Lewis acid employed. As noted above, the ranges given particularly apply to the controlling agents containing one carboxylic acid or sulphonic acid functionality, e.g., those listed as (i) to (iv) above where y or z is equal to 1. For those controlling agents containing more than one acid group per molecule, e.g. where y or z is not 1, the equivalents of controlling agent to acid halide groups in the monomer systems may be adjusted accordingly.
  • controlling agent can produce particles of a smaller mode particle size than the lower amounts of controlling agent. It has been found that controlling the particle size is particularly suited to PAEK copolymers in which the 1,4-linked units are present in 50% or more by weight.
  • controlling agent As well as decreasing the size of the particles produced, increasing the relative amount of controlling agent used can result in extremely small particles being formed. For example, particles of less than one micron, i.e. as small as 0.275 ⁇ m have been recorded. If very small particles are desired, the amount of controlling agent (and/or other factors known to influence particle size in polymerisation reactions) can be chosen to optimise the amount of smaller particles and the smallest particles removed from the product mixture, e.g. by using conventional techniques such as sieving, air classification (e.g. air elutration), photoanalysis, optical counting methods, electroresistance counting methods, sedimentation techniques, laser diffraction methods, acoustic spectroscopy, ultrasound attenuation spectroscopy etc.
  • air classification e.g. air elutration
  • photoanalysis e.g. photoanalysis
  • optical counting methods e.g. electroresistance counting methods
  • sedimentation techniques e.g. laser diffraction methods
  • the present disclosure allows PAEK copolymers of graded particle sizes to be produced. This lends the copolymer to a variety of different applications as the size range of the particles can be controlled to suit the end use. For example, very small (e.g. sub-micron particles) could be used for powder impregnation of composites.
  • the present disclosure provides a method for producing polyaryletherketone copolymers as herein described, having a selected particle size distribution, said method comprising the following steps:
  • the particle size is selected by adjusting the ratio of moles of controlling agent to moles of acid halide groups present in the monomer system.
  • Typical ratios of moles of controlling agent to moles of acid halide groups present in the monomer system are as described herein, e.g. from 0.1 to 10, preferably 0.5 to 7, especially 0.7 to 5, particularly preferably 1.5 to 2.
  • copolymers of the present disclosure are amine-functionalised, e.g. amine terminated.
  • copolymers of the present disclosure are in particulate form.
  • copolymers of the present disclosure are block copolymers.
  • compositions comprising the copolymers as herein described, e.g. spherical particles of amine-functionalised copolymers, may comprise the particles (e.g. spherical particles) of PAEK copolymers in a suitable matrix, for example another polymer, such as a thermoplastic or thermoset.
  • a suitable matrix for example another polymer, such as a thermoplastic or thermoset.
  • the particles can also be utilised as the powders in powder impregnated fibre composites.
  • the polymer particles may be solid, hollow or porous, e.g. porous with an outer shell.
  • these may be used to encapsulate or support materials, e.g. active agents in order to impart extra functionality to the polymer.
  • the cellular structure of particles of the present disclosure can allow penetration of liquid thermoset resin to infuse and react to form an interpenetrating network at the article surface
  • the functional groups of the materials of the present disclosure may be used to attach the polymer (e.g. polymer particles) covalently to other materials, e.g. other polymers and can be used, for example, in the production of toughened polymer materials.
  • polymers of the present disclosure may be blended with other polymers in order to produce polymer blends suited to a variety of purposes.
  • articles comprising the polymers of the present disclosure form a further aspect of the present disclosure.
  • copolymers of the present disclosure are particularly useful for use in structural components, composites, additive layer manufacturing, fibres, films, electrical and medical applications.
  • the present disclosure provides the above processes wherein the controlling agent is a Lewis base.
  • the term "Lewis base” refers to a substance capable of donating an unshared electron pair to a Lewis acid. Mixtures of two or more Lewis bases can be used if desired.
  • a Lewis base in employed as controlling agent the polymer formed is typically a gel.
  • Typical Lewis bases which can be employed include, amides, amines, esters, ethers, ketones, nitriles, nitro compounds, phosphines, phosphine oxides, phosphoramides, sulfides, sulfones, sulfonamides, sulfoxides and halide salts.
  • the Lewis base may be selected from acetone, benzophenone, cyclohexanone, methyl acetate, ethylene carbonate, N-methylformamide, acetamide, N,N-dimethylacetamide, N-methylpyrrolidone, urea, tetramethylurea, N-acetylmorpholine, dimethyl sulfoxide, N,N-dimethylformamide, diphenyl sulfone, N,N-dimethylmethanesulfonamide, phosphoryl chloride, phenylphosphonyl chloride, pyridine-N-oxide, triphenylphosphine oxide, trioctylphosphine oxide, nitropropane, nitrobenzene, benzonitrile, n-butyronitrile, methyl ether, tetrahydrofuran, dimethyl sulfide, trimethylamine, N,N,N',N'-tetramethylethylenediamine, N
  • suitable Lewis bases include inorganic salts which can form complexes with Lewis acids, for example, chlorides, such as trimethylammonium chloride, tetramethylammonium chloride, sodium chloride or lithium chloride, perchlorates, trifluoromethanesulfonates etc.
  • Lewis bases are dimethylsulphone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, tetramethylene sulfone (also known as sulfolane), n-butyronitrile, dimethyl sulfide, imidazole, acetone, benzophenone, trimethylamine, trimethylamine hydrochloride, tetramethylammonium chloride, pyridine-N-oxide, 1-ethylpyridinium chloride, lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide and mixtures thereof.
  • reaction mass Whilst stirring at 450 rpm the reaction mass was warmed to 0°C and maintained for 30 mins. The mass was then warmed to +20°C and maintained for 6 hours. During this period, the colour of the reaction mass was dark orange. During the polymerisation, hydrogen chloride was evolved which was trapped and disposed of safely.
  • reaction mass After stirring at room temperature for 6 hours the reaction mass was poured into 5 litres of iced water (care must be taken to avoid the temperature of the decomplexing mixture rising above room temperature). The aqueous mass was then stirred at room temperature for 4 hours or until all of the orange colouration had disappeared leaving a pale cream mass.
  • the vessel was heated and the dichloromethane distilled off.
  • the yield of the recovered dichloromethane was 92% by weight.
  • the mass was brought to reflux and refluxed for 1 hour whereupon the suspension was filtered whilst hot. While the filtrate was left to cool the white polymer solid was added to a further 3 litres of deionised water containing 300ml of concentrated hydrochloric acid and brought to reflux, the reflux maintained for 1 hour. This was repeated a further two times, without the hydrochloric acid, and in each case the filtrate was added to the initial filtrate and allowed to cool.
  • the polymer powder was refluxed in deionised water containing 100ml of 0.88 ammonia. Finally the polymer powder was refluxed in deionised water with no additives. The polymer powder was then dried overnight at 80°C in air and then at 200°C overnight under vacuum. On cooling, benzoic acid crystallised from the combined filtrates. The yield of benzoic acid was enhanced by chilling the filtrates to 5°C. The yield of the recovered benzoic acid was 77% by weight.
  • the Inherent Viscosity (IV) of the polymer was determined by dissolving approximately 25 mg of the polymer in 25 ml of concentrated sulphuric acid at 25°C. The IV of this sample was 0.92 dL/g. The structure of the polymer was confirmed by 13 C NMR. The presence of amine terminations was confirmed using infra-red spectroscopy.
  • the T g of the polymer was 198°C, no T m was observed.
  • Example 1 was repeated substituting the benzoic acid for dimethyl sulphone where the quantity of dimethyl sulphone was 50.85g (0.5404mol) and the amount of aluminium chloride was 344g (2.58mol).
  • the polymer was isolated as a gel and decomplexed using a Waring blender. None of the dimethyl sulphone was recovered and only 20% of the dichloromethane.
  • the IV of the polymer was 0.97dl/g and the T g 197°C.
  • the polymer was characterised as in example 1.
  • the IV of the polymer was 1.47dL/g.
  • the T g of the polymer was 173°C
  • the IV of the polymer was 0.62dL/g.
  • the T g was 180°C and the T m 344°C
  • Example 4 was repeated replacing the 4,4'-diphenoxybenzophenone with 1,4-bis(4-phenoxybenzoyl)benzene (EKKE): 121.39g (0.258mol)
  • the amount of aluminium chloride used was 434g (3.25mol)
  • the IV of the polymer was 0.64dL/g.
  • the T g was 182°C and the T m 346°C
  • the IV of the resultant polymer was 0.97dL/g
  • the T g of the polymer was 200°C, the T m was 342°C
  • the IV of the polymer was 0.91 dL/g.
  • the T g of the polymer was 185 °C and the T m 362 °C.
  • the T g of the same fully random copolymer was 176 °C and the polymer was essentially amorphous.
  • Example 7 was repeated using the following reagents. This gives an -NH 2 terminated polymer.
  • the IV of the resultant polymer was 0.84dL/g.
  • the T g of the polymer was 186 °C the T m was 360 °C.
  • the random copolymer is essentially amorphous.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Claims (15)

  1. Verfahren zur Herstellung eines Copolymers aus Amin-funktionalisiertem Polyaryletherketon, wobei das Verfahren die Schritte umfasst des:
    Polymerisierens (i) eines Monomer-Systems, das zur Bildung von Aryletherketon-Einheiten geeignet ist, und (ii) eines Comonomers in einem Reaktionsmedium, umfassend:
    (a) eine Lewis-Säure und
    (b) ein Steuermittel, umfassend eine aromatische Carbonsäure, eine aromatische Sulfonsäure, oder ein Derivat davon;
    und
    Zugebens eines Verkappungsmittels, umfassend -NR2, -NRH oder eine geschützte Amingruppe, zu dem Reaktionsmedium, wobei jedes R unabhängig eine aliphatische oder aromatische Gruppe ist.
  2. Verfahren nach Anspruch 1, wobei das Comonomer eine Ester-, Imid-, Sulfon- und/oder Amidgruppe umfasst.
  3. Verfahren nach Anspruch 1 oder Anspruch 2 zum Erzeugen von Block-Copolymeren, wobei das zum Bilden von Aryletherketon-Einheiten geeignete Monomer-System separat zu dem Comonomer polymerisiert wird.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei die Aryletherketon-Einheiten aus dem Folgenden unabhängig ausgewählt werden:
    -AR-O-Ar-C(=O)-
    -AR-O-Ar-C(=O)-Ar-C(=O)-
    -AR-O-Ar-O-Ar-C(=O)-
    -AR-O-Ar-O-Ar-C(=O)-Ar-C(=O)-
    -AR-O-Ar-C(=O)-Ar-O-Ar-C(=O)-Ar-C(=O)-
    wobei jedes Ar unabhängig ein aromatischer Teil ist.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei das Steuermittel eines oder mehrere ist von

            (i)     Ar'(COOX)y;

            (ii)     Ar'(SO3X)y;

            (iii)     (Ar'COO-)zMz+; oder

            (iv)     (Ar'SO3 -)zMz+

    wobei Ar' eine aromatische Gruppe ist, die mit den verbleibenden Komponenten des Reaktionsmediums kompatibel ist;
    jedes X unabhängig ein Wasserstoffatom oder eine organische Gruppe ist;
    jedes y unabhängig 1, 2 oder 3 ist;
    jedes M unabhängig ein Metallion ist und
    jedes z unabhängig eine ganze Zahl gleich der Ladung auf dem Metallion (Mz+) ist.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei das Verkappungsmittel von der Formel (Z)a-Ar-(X)b ist, wobei
    jedes X unabhängig ausgewählt wird aus -O-Ar, -C(=O)Cl, -C(=O)-Ar-O-Ar und -O-Ar-[-C(=O)-Ar-O-Ar-]c-H, wobei jedes Ar unabhängig ein aromatischer Teil ist;
    c eine ganze Zahl ist;
    Z eine geschützte Amingruppe ist;
    jede R-Gruppe unabhängig eine aliphatische oder aromatische Gruppe ist;
    a 1 bis 5 ist; und
    b 1 bis 5 ist.
  7. Verfahren nach einem der Ansprüche 4 bis 6, wobei jedes Ar unabhängig ausgewählt wird aus substituierten und unsubstituierten mononuklearen aromatischen Teilen und substituierten und unsubstituierten polynuklearen aromatischen Teilen.
  8. Verfahren nach einem der vorstehenden Ansprüche, wobei das Verkappungsmittel ist:
    Figure imgb0056
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei das Reaktionsmittel zwei oder mehrere Arten von Comonomer umfasst.
  10. Partikel eines Copolymers aus Amin-funktionalisiertem Polyaryletherketon, wobei das Copolymer wie in einem der Ansprüche 1 bis 9 beschrieben ist.
  11. Block-Copolymer aus Amin-funktionalisiertem Polyaryletherketon, wobei das Copolymer wie in einem der Ansprüche 1 bis 9 beschrieben ist.
  12. Copolymere aus Amin-funktionalisiertem Polyaryletherketon, die Polymere sind, die einen oder mehrere Arten von Aryletherketon-Einheit und eine oder mehrere Arten von Nicht-Aryletherketon-Einheit umfassen und wobei das Copolymer weder ein Aminfunktionalisiertes PEK-Imid-Copolymer noch ein Amin-funktionalisiertes PEK-Sulfon-Copolymer ist.
  13. Copolymer nach Anspruch 11 oder Anspruch 12, wobei das Copolymer in partikulärer Form vorliegt.
  14. Copolymer nach Anspruch 10 oder Anspruch 12, wobei das Copolymer ein Block-Copolymer ist.
  15. Verfahren oder Copolymer nach einem der vorstehenden Ansprüche, wobei das Amin-funktionalisierte Copolymer ein Amin-terminiertes Copolymer ist.
EP15728081.9A 2014-05-22 2015-05-21 Copolymere aus amin-derivatisiertem polyaryletherketon Active EP3145975B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1409128.4A GB201409128D0 (en) 2014-05-22 2014-05-22 Method
PCT/GB2015/051488 WO2015177550A1 (en) 2014-05-22 2015-05-21 Amine and non-amine derivatised polyaryletherketone random and block copolymers

Publications (2)

Publication Number Publication Date
EP3145975A1 EP3145975A1 (de) 2017-03-29
EP3145975B1 true EP3145975B1 (de) 2021-03-17

Family

ID=51177295

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15728081.9A Active EP3145975B1 (de) 2014-05-22 2015-05-21 Copolymere aus amin-derivatisiertem polyaryletherketon

Country Status (4)

Country Link
US (1) US10800876B2 (de)
EP (1) EP3145975B1 (de)
GB (1) GB201409128D0 (de)
WO (1) WO2015177550A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10011685B2 (en) 2016-03-11 2018-07-03 The Boeing Company Polyarylether ketone imide adhesives
US9976063B2 (en) * 2016-03-11 2018-05-22 The Boeing Company Polyarylether ketone imide sulfone adhesives
KR102250301B1 (ko) * 2018-12-12 2021-05-07 한화솔루션 주식회사 결정화 속도가 향상된 폴리에테르케톤케톤 제조방법 및 이에 의해 제조된 폴리에테르케톤케톤

Family Cites Families (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065205A (en) 1959-10-27 1962-11-20 Du Pont Aromatic polyketones and preparation thereof
US3288855A (en) 1963-03-25 1966-11-29 Monsanto Res Corp Fluorinated diones
US3953400A (en) 1972-01-17 1976-04-27 Raychem Corporation Polyketones and methods therefor
US4698393A (en) 1983-03-31 1987-10-06 Raychem Corporation Preparation of poly(arylene ether ketones)
US4808693A (en) * 1984-08-20 1989-02-28 Raychem Corporation Aryl ether ketone copolymers
ES8704521A1 (es) 1984-09-06 1987-04-16 Raychem Corp Metodo de preparacion de una poli(arileno eter cetona)
GB8521324D0 (en) * 1985-08-27 1985-10-02 Raychem Ltd Preparation of monomers
AU589146B2 (en) 1984-10-11 1989-10-05 Raychem Limited Aromatic poly(ether ketones)
US4816556A (en) 1985-02-22 1989-03-28 E. I. Du Pont De Nemours And Company Ordered polyetherketones
US4786694A (en) * 1985-05-02 1988-11-22 Amoco Corporation Poly(aryl ether ketone) block copolymers
US4861915A (en) * 1985-05-02 1989-08-29 Amoco Corporation Poly (aryl ether ketone) block copolymers
US4837284A (en) * 1985-10-15 1989-06-06 Amoco Corporation Novel poly(aryl ether ketone)-polyester block copolymers
DE3602090A1 (de) * 1986-01-24 1987-07-30 Basf Ag Verfahren zur herstellung von aromatischen block-copolyethern
GB8608870D0 (en) * 1986-04-11 1986-05-14 Raychem Ltd Aromatic polyketones & polysulphones
US4959424A (en) 1986-07-25 1990-09-25 Amoco Corporation Amino-terminated poly(aryl ether ketones)
US5137988A (en) * 1986-07-25 1992-08-11 Amoco Corporation Amino-terminated poly(aryl ether ketones)
US4841013A (en) 1986-09-18 1989-06-20 Raychem Limited Preparation of poly(arylene ether ketones)
GB8623510D0 (en) 1986-09-30 1986-11-05 Raychem Ltd Aryl carbonyl compounds
GB8623511D0 (en) * 1986-09-30 1986-11-05 Raychem Ltd Arylene cligomers
GB8702993D0 (en) * 1987-02-10 1987-03-18 Ici Plc Aromatic polymer
US4843131A (en) 1987-10-20 1989-06-27 Raychem Corporation Preparation of poly(arylene ether ketones) by sequential oligomerization and polymerization in distinct reaction zones
US4912181A (en) 1987-10-20 1990-03-27 Raychem Corporation Preparation of poly(arylene ether ketones) by sequential oligomerization and polyerization in distinct reaction zones
GB8725886D0 (en) * 1987-11-04 1987-12-09 Raychem Ltd Poly(ar-lene ether ketones)
GB8726884D0 (en) * 1987-11-17 1987-12-23 Raychem Ltd Poly(arylene ether ketones)
US5260404A (en) 1988-04-19 1993-11-09 Raychem Limited Polyetherketonimides
GB8815976D0 (en) * 1988-07-05 1988-08-10 Raychem Ltd Ethersulphone polymers
US5084530A (en) * 1988-08-22 1992-01-28 Amoco Corporation Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers
US4962143A (en) * 1988-10-25 1990-10-09 Kureha Kagaku Kogyo K.K. Poly(arylene thioether) block copolymer fibers and production process thereof
DE4012589A1 (de) * 1990-04-20 1991-10-24 Hoechst Ag Thermoplastisch weiterverarbeitbare folie aus aromatischem polyetherketon
GB9023365D0 (en) * 1990-10-26 1990-12-05 Raychem Ltd Aryl-ether-sulphone monomers and aryl-ether-ketone-sulphone polymers
GB9023363D0 (en) * 1990-10-26 1990-12-05 Raychem Ltd Ether-ketone-sulphone copolymers
GB9403944D0 (en) 1994-03-02 1994-04-20 Victrex Manufacturing Ltd Aromatic polymers
DE69630358T2 (de) * 1995-12-26 2004-07-29 Teijin Ltd. Anwendung von Sulfongruppen enthaltenden Polyalkylenethern in medizinischen Materialien
JP3814881B2 (ja) * 1996-08-07 2006-08-30 味の素株式会社 シクロヘキシルアミノ酸類の製造方法
GB9803714D0 (en) * 1998-02-24 1998-04-15 Cytec Tech Corp Process for preparing polymers
GB0015433D0 (en) 2000-06-24 2000-08-16 Victrex Mfg Ltd Bio-compatible polymeric materials
US8568705B2 (en) * 2005-07-18 2013-10-29 Nektar Therapeutics Method for preparing branched functionalized polymers using branched polyol cores
CN100374483C (zh) * 2006-03-29 2008-03-12 长春吉大高科技股份有限公司 聚醚醚砜和聚醚醚酮三元共聚物的制备方法
KR100744380B1 (ko) * 2006-04-17 2007-07-30 삼성전자주식회사 외부 디스플레이 장치로 영상을 출력할 수 있는 기능을구비한 이동 단말기에서의 디스플레이 제어 장치 및 방법
FR2909675B1 (fr) * 2006-12-08 2012-10-12 Arkema France Copolymere a blocs polyamide, polyester et polyether
WO2009057255A1 (ja) * 2007-10-31 2009-05-07 Kaneka Corporation ポリエーテルエーテルケトン、及び、ポリマー材料の精製方法
US20110213115A1 (en) * 2008-10-24 2011-09-01 Solvay Advanced Polymers, L.L.C. Process for preparing a poly(aryl ether ketone) using a high purity 4,4'-difluorobenzophenone
GB0911905D0 (en) 2009-07-09 2009-08-19 Ketonex Ltd Method
GB201117796D0 (en) * 2011-10-14 2011-11-30 Victrex Mfg Ltd Polymeric materials
CN102875819B (zh) 2012-10-29 2014-05-07 吉林大学 芳香族聚醚醚酮-聚酰亚胺嵌段共聚物、制备方法及其应用
EP2931787A2 (de) 2012-12-17 2015-10-21 Solvay Specialty Polymers USA, LLC. Polyaryletherpolymere mit phenolischen aminosäuren als endgruppen
GB201311376D0 (en) * 2013-06-26 2013-08-14 Victrex Mfg Ltd Polymetric Materials
GB201311952D0 (en) * 2013-07-03 2013-08-14 Victrex Mfg Ltd Polymetric Materials
GB201409126D0 (en) * 2014-05-22 2014-07-09 Ketonex Ltd Process
JP6637491B2 (ja) * 2014-05-22 2020-01-29 サイテック インダストリーズ インコーポレイテッド 粒状アミン官能化ポリアリールエーテルケトンポリマー及びそのコポリマー
GB201415972D0 (en) * 2014-09-10 2014-10-22 Ketonex Ltd Process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US10800876B2 (en) 2020-10-13
WO2015177550A1 (en) 2015-11-26
EP3145975A1 (de) 2017-03-29
US20170081467A1 (en) 2017-03-23
GB201409128D0 (en) 2014-07-09

Similar Documents

Publication Publication Date Title
CA2949718C (en) Particulate amine-functionalized polyaryletherketone polymer and copolymers thereof
CA2949924C (en) Method for making particulate amine-functionalized polyaryletherketone polymers and copolymers thereof
CA2804687C (en) Method for preparing poly (ether ketone ketones)
EP0124276B1 (de) Herstellung von aromatischen Polymeren
US10800876B2 (en) Amine and non-amine derivatized polyaryletherketone random and block copolymers
US10450408B2 (en) Method for making polyarylaliphaticetherketone polymers and copolymers thereof
JPH0676491B2 (ja) エーテル―ケトン―イミド芳香族ポリマー
AU589146B2 (en) Aromatic poly(ether ketones)
JPH02248424A (ja) 芳香族ポリマー
WO2015177551A1 (en) Particulate aromatic poly(ether ketone ether ketone ketones)
JPH01259029A (ja) 芳香族ポリエーテルケトン

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161216

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200618

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20210208

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015066951

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1372199

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210415

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210617

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210617

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210618

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1372199

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210317

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210717

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210719

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015066951

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210521

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210531

26N No opposition filed

Effective date: 20211220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250519

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20260326

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20260330

Year of fee payment: 12